Photosensitive resin composition, photosensitive element using the same, method for producing resist pattern, resist pattern and substrate having the resist pattern laminated thereon

ABSTRACT

Disclosed are a photosensitive resin composition comprising a photosensitive resin (A), a photopolymerization initiator (B), and a flame retardant (C), in which a content of halogen atoms or antimony atoms in the flame retardant is 5% or less by weight; a photosensitive element using this; a method of manufacturing a resist pattern; a resist pattern; and a resist pattern laminated substrate.

TECHNICAL FIELD

The present invention relates to a photosensitive resin composition, aphotosensitive element using this, a method of manufacturing a resistpattern, a resist pattern, and a resist pattern laminated substrate.

BACKGROUND ART

Conventionally, solder mask resists in the manufacturing of printedwiring boards have been produced by the screen printing of thermosettingor ultraviolet-curing resist inks.

As electronic devices are becoming highly-integrated, higher precisionin the wiring and insulation patterns of printed wiring boards isrequired, and it is difficult to form high precision resist images usingthe conventional production method of screen printing, due to theoccurrence of smears and drips.

Therefore, a method of forming resist images using photolithography hasbeen developed and various inks such as solder resists and markingresists have been improved from the conventional thermosetting type to aphotosensitive type capable of image formation.

Furthermore, in the field of electric and electronic materials such asprinted wiring boards and semiconductors, materials are required, withthe aim of creating a better working environment and protecting theglobal environment, to be flame-retardant but free from halogen-basedcompounds and antimony-based compounds which can harm the environment.These requirements also apply to a photosensitive solder mask resist, asone of these electric and electronic materials. However, nophotosensitive solder mask resist that is non-halogen-based,non-antimony-based with sufficient flame retardancy has as yet beendeveloped. Therefore, problems have arisen where for example, when anon-halogen-based, non-antimony-based substrate and a solder resist areused in combination to manufacture a non-halogen printed wiring board,the resultant printed wiring board has not met flame retardancystandards because of the inflammability of the solder resist, despitethe flame retardancy of the substrate.

DISCLOSURE OF INVENTION

It is an object of the present invention to provide a flame-retardantphotosensitive resin composition to be used suitably in realizingnon-halogen type manufacturing of printed wiring boards, semiconductorpackages, and the like; which can yield a solder resist cured filmsuperior in flame retardancy as well as heat resistance, mechanicalcharacteristics, adhesion, and chemical resistance.

It is another object of the present invention to provide aphotosensitive element to be used suitably in realizing non-halogen typemanufacturing of printed wiring boards, semiconductor packages, and thelike; which can yield a solder resist cured film superior in flameretardancy as well as heat resistance, mechanical characteristics,adhesion, chemical resistance, workability, and productivity.

It is yet another object of the present invention to provide a resistpattern, its manufacturing method, and a resist pattern laminatedsubstrate to be used suitably in realizing non-halogen typemanufacturing of printed wiring boards, semiconductor packages, and thelike; which is superior in flame retardancy as well as heat resistance,mechanical characteristics, adhesion, chemical resistance, workability,and productivity.

According to the first aspect of the present invention, there isprovided a photosensitive resin composition comprising a photosensitiveresin (A), a photopolymerization initiator (B), and a flame retardant(C), in which a content of halogen atoms or antimony atoms in the flameretardant is 5% or less by weight. According to the second aspect of thepresent invention, there is provided a photosensitive resin compositioncomprising a photosensitive resin (A), a photopolymerization initiator(B), and a zinc compound (C1). According to the third aspect of thepresent invention, there is provided a photosensitive resin compositioncomprising a photosensitive resin (A), a photopolymerization initiator(B), and an organic nitrogen-based compound (C2). According to thefourth aspect of the present invention, there is provided aphotosensitive resin composition comprising a photosensitive resin (A),a photopolymerization initiator (B), and a metal hydroxide (C3).According to the fifth aspect of the present invention, there isprovided a photosensitive resin composition comprising a photosensitiveresin (A), a photopolymerization initiator (B), and an organicphosphorus-based compound (C4).

By adopting each constituent, the photosensitive resin compositionaccording to the present invention is superior in flame retardancy inspite of being substantially free from halogens and antimony, whichallows the photosensitive resin composition to be used suitably inrealizing non-halogen type manufacturing of printed wiring boards,semiconductor packages, and the like, and use of the photosensitiveresin composition yields a solder resist cured film superior in flameretardancy as well as heat resistance, mechanical characteristics,adhesion, and chemical resistance.

According to another aspect of the present invention, there is provideda photosensitive element obtained by forming a resist layer formed bythe photosensitive resin composition according to the present inventiononto a substrate. This photosensitive element employs the photosensitiveresin composition according to the present invention as a resist layer,which can yield a solder resist cured film superior in flame retardancyas well as heat resistance, mechanical characteristics, adhesion,chemical resistance, workability, and productivity and which can be usedsuitably in realizing non-halogen type manufacturing of printed wiringboards, semiconductor packages, and the like.

According to yet another aspect of the present invention, amanufacturing method of a resist pattern comprising the following stepsis provided:

-   -   i) a step of laminating a resist layer formed by the        photosensitive resin composition according to the present        invention onto a substrate;    -   ii) a step of irradiating active rays in an image shape to        photo-cure the resist layer at exposed portions; and    -   iii) a step of selectively removing the resist layer at        unexposed portions by development, to form a resist pattern.

According to yet another aspect of the present invention, a resistpattern produced by the above-mentioned manufacturing method of a resistpattern is provided. Using the above-mentioned manufacturing method of aresist pattern, it is possible to obtain a resist pattern which issuperior in flame retardancy as well as heat resistance, mechanicalcharacteristics, adhesion, chemical resistance, workability, andproductivity and which can be used suitably in realizing non-halogentype manufacturing of printed wiring boards, semiconductor packages, andthe like.

According to yet another aspect of the present invention, a resistpattern laminated substrate is obtained by laminating a resist patternobtained by using a resist layer formed by the photosensitive resincomposition according to the present invention onto a substrate. Thislaminated substrate employs the photosensitive resin compositionaccording to the present invention as a resist layer, and therefore issuperior in flame retardancy as well as heat resistance, mechanicalcharacteristics, adhesion, chemical resistance, workability, andproductivity and can be used suitably in realizing non-halogen typemanufacturing of printed wiring boards, semiconductor packages, and thelike.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic drawing which shows an embodiment of aphotosensitive element.

FIGS. 2A, 2B and 2C comprise a schematic drawing which shows an exampleof steps of the manufacturing method of a resist pattern.

BEST MODE FOR CARRYING OUT THE INVENTION

Embodiments of the present invention will be described in detailhereinafter. In the following description, (meth)acrylic acid refers toacrylic acid and corresponding methacrylic acid, (meth)acrylate refersto acrylate and corresponding methacrylate, and (meth)acryloyl grouprefers to methacryloyl group and corresponding methacryloyl group.

The photosensitive resin composition according to the present invention(hereinafter referred to as ‘composition X’) comprises a photosensitiveresin (A), a photopolymerization initiator (B), and a flame retardant(C), in which a content of halogen atoms or antimony atoms in theabove-mentioned flame retardant is 5% or less by weight. Here, thecontent of halogen atoms or antimony atoms in the above-mentioned flameretardant is the amount of either or both halogen atoms and antimonyatoms in the molecule, relative to the molecular weight of the flameretardant, in which the amount of halogen atoms or antimony atomspresent in the flame retardant as impurities (for example, halogen atomsor antimony atoms in the catalyst used in the synthesis of the flameretardant compound) is not included. When the content of halogen atomsor antimony atoms in the above-mentioned flame retardant is 5% or lessby weight, a flame-retardant photosensitive resin composition becomessubstantially halogen- and antimony-free so that there is no damagingimpact on the environment. The content of halogen atoms or antimonyatoms in the flame retardant is preferably 3% or less by weight, morepreferably 1% by weigh or less, even more preferably 0.5% or less byweight, and still more preferably 0.1% or less by weight. Mostpreferably, a flame retardant that contains neither halogen atoms norantimony atoms is used.

The flame retardancy of the photosensitive resin composition X ispreferably such that it can impart flame retardancy which satisfiesUL94V-0 or V-1 in UL94V standards to a laminate formed by laminating a50 μm thick layer of the photosensitive resin composition to the bothsides of a 0.3 mm thick non-halogen copper-clad laminate. When this isthe case, it is possible to provide a highly flame-retardant printedwiring board, by using it in combination with a non-halogen substrate,for example. Here, the above-mentioned non-halogen copper-clad laminateis ‘MCR—RO-67G’ manufactured by Hitachi Chemical Co., Ltd.

A photosensitive resin composition according to another aspect of thepresent invention (hereinafter referred to as ‘composition I’) comprisesa photosensitive resin (A), a photopolymerization initiator (B), and azinc compound (C1).

A photosensitive resin composition according to another aspect of thepresent invention (hereinafter referred to as ‘composition II’)comprises a photosensitive resin (A), a photopolymerization initiator(B), and an organic nitrogen-based compound (C2).

A photosensitive resin composition according to another aspect of thepresent invention (hereinafter referred to as ‘composition III’)comprises a photosensitive resin (A), a photopolymerization initiator(B), and a metal hydroxide (C3).

A photosensitive resin composition according to another aspect of thepresent invention (hereinafter referred to as ‘composition IV’)comprises a photosensitive resin (A), a photopolymerization initiator(B), and an organic phosphorus-based compound (C4).

The compositions I to IV preferably have the same characteristics of thecontent of halogen atoms and antimony atoms and the flame retardancy asdescribed for the above-mentioned composition X.

Each component will be described hereinafter.

No limitation is imposed on a photosensitive resin (A) provided it has aphotosensitive group. The photosensitive resin can be obtained, forexample, by reacting a reaction product (A′) of epoxy resin (a1) andunsaturated group-containing monocarboxylic acid (a2), with anhydride(a3) of saturated or unsaturated group-containing polybasic acid. Inthis case, it is believed that an epoxy group of the epoxy resin (a1)and a carboxylic group of the unsaturated group-containingmonocarboxylic acid (a2) undergo an addition reaction in the firstreaction to form a hydroxyl group, and the resultant hydroxyl group andan anhydride group of the anhydride (a3) of saturated or unsaturatedgroup-containing polybasic acid undergo a half-ester reaction in thenext reaction.

Examples of the above-mentioned epoxy resin (a1) include novolac-typeepoxy resins, bisphenol-type epoxy resins, salicylic aldehyde-type epoxyresins, and rubber-modified epoxy resins. These compounds may be usedsingly or with two or more in combination.

Examples of the novolac-type epoxy resins preferably include phenolnovolac-type epoxy resins, cresol novolac-type epoxy resins, and epoxyresins represented by the general formula (XII):

(wherein X represents a hydrogen atom or a glycidyl group; each one ofR⁴² to R⁴⁴ independently represents a hydrogen atom or an alkyl groupwith 1–5 carbon atoms; and k¹ is an integer greater than or equal to 1).

The above-mentioned phenol novolac-type epoxy resins and cresolnovolac-type epoxy resins can be obtained, for example, by reactingphenol novolac resins or cresol novolac resins with epichlorohydrin.

Examples of available novolac-type epoxy resins include EOCN-102S,EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027, EOCN-100,EOCN-3300, EOCN-4400, EP PN-201, RE-305, RE-306 (product names of NipponKayaku Co., Ltd.), YDPN-638, YDPN-638P, YDCN-701, YDCN-702, YDCN-703,YDCN-704, YDCN-500 (product names of Tohto Kasei Corporation),ESCN-195XL, ESCN-195XF, ESCN-195×HH, ESCN-220L, ESCN-220F, ESCN-220HH,ESCN-200L (product names of Sumitomo Chemical Co., Ltd.), ‘EPICLON’series of N-660, N-665, N-667, N-670, N-673, N-680, N-690, N-695,N-665EXP, N-673-70M, N-680-75M, N-690-75M, N738, N-740, N-770, N-775,N-770-70M, N-865, and N-86570M (product names of Dainippon Ink andChemicals, Incorporated). These compounds may be used singly or with twoor more in combination.

Examples of the above-mentioned bisphenol-type epoxy resins preferablyinclude bisphenol A-type epoxy resins, bisphenol F-type epoxy resins,bisphenol S-type epoxy resins, and epoxy resins represented by thegeneral formula (XIII):

(wherein X has the same meaning as X in the general formula (XII); Yrepresents —CH₂—, —C(CH₃)₂—, or —SO₂—; R⁴⁵ to R⁶⁰ have the same meaningas R⁴² in the general formula (XII); and k² is an integer greater thanor equal to 1). These compounds may be used singly or with two or morein combination.

As the above-mentioned bisphenol-type epoxy resin, for example, acompound obtained by reacting a hydroxyl group of bisphenol-type resinwith epichlorohydrin can be used.

The reaction is preferably conducted in a polar organic solvent such asdimethylformamide, dimethylacetoamide, and dimethylsulfoxide in thepresence of an alkali metal hydroxide at a reaction temperature of about50° C. to about 120° C. to accelerate the reaction of the hydroxyl groupand epichlorohydrin. When the reaction temperature is below 50° C., thereaction tends to be slow, and when the temperature exceeds 120° C.,more side reactions tend to occur.

Examples of available bisphenol-type epoxy resins include RE-310S,RE-304S, RE-404S (product names of Nippon Kayaku Co., Ltd.), YD-115,YD-115G, YD-115CA, YD-118P, YD-127, YD-128, YD-128G, YD-128S, YD-128CA,YD-134, YD-134N, YD-011, YD-012, YD-013, YD-014, YD-017, YD-019, YD-020,YD-8125, YD-7011R, YD-7014R, YD-7017, YD-7019, YD-7020, YD-900, YD-901,YD-902, YD-903, YD-904, YD-907, YD-909, YD-927H, ZX-1059, YDF-8170,YDF-170, YDF-175S, YDF-2001, YDF-2004 (product names of Tohto KaseiCorporation), EPICLON series of 840, 840S, 850, 850S, 850CRP, 855, 857,D-515, 860, 900IM, 1050, 1055, 2055, 3050, 4050, 4055, 7050, 9055, 830,830S, 830LVP, 835, 835LV, EXA-1514, and EXA-4004 (product names ofDainippon Ink and Chemicals, Incorporated). These compounds may be usedsingly or with two or more in combination.

The above-mentioned salicylic aldehyde-type epoxy resins can beobtained, for example, by reacting a reaction product of salicylicaldehyde and phenol or cresol (salicylic aldehyde-type resin) withepichlorohydrin, and preferably include epoxy resins represented by thegeneral formula (XIV):

(wherein X has the same meaning as X in the general formula (XII); R⁶¹to R⁶⁵ have the same meaning as R⁴² in the general formula (XII); and k³is an integer greater than or equal to 1).

Examples of available salicylic aldehyde-type epoxy resins includeEPPN-501H, EPPN-501HY, EPPN-502H, and FAE-2500 (product names of NipponKayaku Co., Ltd.). These compounds may be used singly or with two ormore in combination.

The above-mentioned rubber-modified epoxy resins can be obtained, forexample, by modifying a part or all of the epoxy groups of theabove-mentioned bisphenol F-type epoxy resins, bisphenol A-type epoxyresins, bisphenol S-type epoxy resins, salicylic aldehyde-type epoxyresins, phenol novolac-type epoxy resins, cresol novolac-type epoxyresins, and the like with butadiene-acrylonitrile rubber modified bycarboxylic acid at both terminals (for example, CTBN, Hycar CTB and thelike manufactured by Goodrich Corp.), silicone rubber having anamino-modified terminal, and the like.

Examples of available rubber modified epoxy resins include epoxydatedpolybutadiene modified epoxy resin: EPOLEAD PB3600, PB4700 (productnames of Daicel Chemical Industries, Ltd.), EPB-13, EPB-1054 (productnames of Nippon Soda Co., Ltd.), epoxydated butadiene-styrene modifiedepoxy resin: EPOFRIEND AT014, AT015, AT000 (product names of DaicelChemical Industries, Ltd.), epoxy compounds of polydimethylsiloxane:X22-163B, KF100T (product names of Shin-Etsu Silicon Co., Ltd.), epoxycompounds obtained by reacting the above-mentioned epoxy compound withan α,ω-polybutadiene dicarboxylic acid, and epoxy compounds obtained byreacting part of the above-mentioned bisphenol F-type epoxy resins,bisphenol A-type epoxy resins, and bisphenol S-type epoxy resins withacrylonitrile-butadiene rubber modified by carboxylic acid at bothterminals. These compounds may be used singly or with two or more incombination.

The bisphenol F-type epoxy resins and rubber-modified epoxy resins arepreferred among these epoxy resins (a1) in view of their mechanicalproperties, adhesion, and development properties.

Furthermore, for example, hydrogenated bisphenol A-type epoxy resins andthe like can be used as a part of the component (a1) as required.

Examples of the unsaturated group-containing monocarboxylic acid (a2)include acrylic acid, a dimer of acrylic acid, methacrylic acid,β-furfurylacrylic acid, β-styrylacrylic acid, cinnamic acid, crotonicacid, α-cyanocinnamic acid, half-ester compounds which are reactionproducts of hydroxyl group-containing acrylate and saturated orunsaturated dibasic acid anhydride, and half-esters which are reactionproducts of unsaturated group-containing monoglycidyl ether andsaturated or unsaturated dibasic acid anhydride. These compounds may beused singly or with two or more in combination.

The above-mentioned half-esters can be obtained, for example, byreacting hydroxyl group-containing acrylate or unsaturatedgroup-containing monoglycidyl ether with saturated or unsaturateddibasic acid anhydride in an equal mol ratio.

Examples of the hydroxyl group-containing acrylate and the unsaturatedgroup-containing monoglycidyl ether include hydroxyethyl acrylate,hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropylmethacrylate, hydroxybutyl acrylate, hydroxybutyl methacrylate,polyethylene glycol monoacrylate, polyethylene glycol monomethacrylate,trimethylol propane diacrylate, trimethylol propane dimethacrylate,pentaerythritol triacrylate, pentaerythritol trimethacrylate,dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate,glycidyl acrylate, and glycidyl methacrylate. These compounds may beused singly or with two or more in combination.

Examples of the above-mentioned saturated or unsaturated dibasic acidanhydride include succinic anhydride, maleic anhydride,tetrahydrophthalic anhydride, phthalic anhydride,methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride,hexahydrophthalic anhydride, methylhexahydrophthalic anhydride,ethylhexahydrophthalic anhydride, and itaconic anhydride. Thesecompounds may be used singly or with two or more in combination.

Furthermore, polybasic acid anhydride such as trimellitic anhydride,pyromellitic anhydride, benzophenonetetracarboxylic acid anhydride, andbiphenyltetracarboxylic acid anhydride can be used as a part of thecomponent (a2) as required.

In the above-mentioned reaction of the component (a1) and the component(a2), 0.8 to 1.05 equivalent, and more preferably 0.9 to 1.0 equivalentof the unsaturated group-containing monocarboxylic acid (a2) ispreferably reacted relative to one equivalent of the epoxy group of theepoxy resin (a1).

Furthermore, the component (a1) and the component (a2) can be reacted,for example, in an organic solvent. Examples of the organic solventinclude ketones such as methyl ethyl ketone and cyclohexanone; aromatichydrocarbons such as toluene, xylene, and tetramethylbenzene; glycolethers such as methyl cellosolve, butyl cellosolve, methyl carbitol,butyl carbitol, propylene glycol monomethyl ether, dipropylene glycolmonoethyl ether, dipropylene glycol diethyl ether, and triethyleneglycol monoethyl ether; esters such as ethyl acetate, butyl acetate,butyl cellosolve acetate, and carbitol acetate; aliphatic hydrocarbonssuch as octane and decane; petroleum solvents such as petroleum ether,petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha.These compounds may be used singly or with two or more in combination.

Furthermore, a catalyst is preferably used to accelerate the reaction ofthe component (a1) and the component (a2), and examples of the catalystinclude triethylamine, benzylmethylamine, methyltriethylammoniumchloride, benzyltrimethylammonium chloride, benzyltrimethylammoniumbromide, benzyltrimethylammonium iodide, and triphenylphosphine. Thesecompounds may be used singly or with two or more in combination. Thecatalyst is preferably used in an amount of about 0.1 to about 10 partsby weight based on 100 parts by weight of the total of the component(a1) and the component (a2).

Furthermore, a polymerization inhibitor is preferably used in order toinhibit the polymerization of the component (a1) and the component (a2)during the reaction, and examples of the polymerization inhibitorinclude hydroquinone, methylhydroquinone, hydroquinone monomethyl ether,catechol, and pyrogallol. These compounds may be used singly or with twoor more in combination. The polymerization inhibitor is preferably usedin an amount of about 0.01 to about 1 parts by weight based on 100 partsby weight of the total of the component (a1) and the component (a2).

The temperature of the reaction of the above-mentioned component (a1)and component (a2) is preferably about 60° C. to about 150° C., and morepreferably about 80° C. to about 120° C.

Examples of the saturated or unsaturated group-containing polybasic acidanhydride (a3), which is to be reacted with the reaction product A′ ofthe component (a1) and the component (a2), include succinic anhydride,maleic anhydride, tetrahydrophthalic anhydride, phthalic anhydride,methyltetrahydrophthalic anhydride, ethyltetrahydrophthalic anhydride,hexahydrophthalic anhydride, methylhexahydrophthalic anhydride,ethylhexahydrophthalic anhydride, and itaconic anhydride. Thesecompounds may be used singly or with two or more in combination.

In the reaction of the reaction product (A′) and the component (a3), theacid value of the photosensitive resin (A) can be adjusted by reacting0.1 to 1.0 equivalent of the component (a3) relative to one equivalentof the hydroxyl group of the reaction product (A′).

The acid value of the photosensitive resin (A) is preferably 30 mgKOH/gor more in view of the solubility of the photosensitive resincomposition in a dilute alkali solution, preferably 150 mgKOH/g or lessin view of the electric properties of the resultant cured film, and morepreferably 50 to 120 mgKOH/g.

The temperature of reaction of the reaction product (A′) and thecomponent (a3) is preferably about 60° C. to about 120° C.

Although methods of obtaining the photosensitive resin (A) using anepoxy resin as a raw material have been described, commerciallyavailable photosensitive resins such as ZFR1122 and ZFR1179 (productnames of Nippon Kayaku Co., Ltd.) can also be used as the photosensitiveresin (A). Furthermore, styrene-maleic acid-based resin such ashydroxyethyl acrylate-modified styrene-maleic anhydride copolymer orhydroxyethyl methacrylate-modified styrene-maleic anhydride copolymercan be used as a part of the photosensitive resin (A). The component (A)is preferably incorporated in an amount of 10 to 90% by weight based onthe total amount of the photosensitive resin composition.

The photopolymerization initiator (B) will be described hereinafter.

Examples of the photopolymerization initiator (B) include benzoins suchas benzoin, benzoin methyl ether, and benzoin isopropyl ether;acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone,2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone,1-hydroxycyclohexyl phenyl ketone,2-methyl-1-[4(methylthio)phenyl]-2-morpholino-1-propanone, andN,N-dimethylaminoacetophenone: anthraquinones such as2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone,1-chloroanthraquinone, 2-amylanthraquinone, and 2-aminoanthraquinone;thioxanthones such as 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone,2-chlorothioxanthone, and 2,4-diisopropylthioxanthone; ketals such asacetophenone dimethyl ketal and benzyl dimethyl ketal; benzophenonessuch as benzophenone, methylbenzophenone, 4,4′-dichlorobenzophenone,4,4′-bisdiethylaminobenzophenone, Michler's ketone, and4-benzoyl-4′-methyldiphenylsulfide; and2,4,6-trimethylbenzoyldiphenylphosphine oxide. These compounds may beused singly or with two or more in combination.

The photosensitive resin composition of the present invention maycontain a photopolymerization initiator auxiliary as required. Examplesof the photopolymerization initiator include tertiary amines such asethyl N,N-dimethylaminobenzoate, isoamyl N,N-dimethylaminobenzoate,pentyl-4-dimethylaminobenzoate, triethylamine, and triethanolamine.These compounds may be used singly or with two or more in combination.

The component (B) is preferably included in an amount of 0.5% or more byweight in order to ensure the photopolymerizability of thephotosensitive resin, preferably 20% or less by weight in view of theheat resistance of the resultant cured material, and more preferably 2to 15% by weight, based on the total amount of the photosensitive resincomposition. When the content of the photopolymerization initiator isbelow 0.5% by weight, unexposed portions are prone to dissolve duringdevelopment.

The flame retardant (C) will next be described. Any flame retardant canbe used provided it's content of halogen atoms or antimony atoms is 5%or less by weight and that it can impart necessary flame retardancy tothe photosensitive resin composition. Although compounds that do notcontain halogen atoms or antimony atoms in the molecule are especiallypreferable, the flame retardant may contain these atoms as substituentsor the like up to the above-mentioned limit.

Preferred flame retardants include, for example, a zinc compound (C1),an organic nitrogen-based compound (C2), a metal hydroxide (C3), and anorganic phosphorus-based compound (C4). These compounds may be usedsingly or with two or more in combination.

The above-mentioned zinc compound (C1) is used as an essential componentof the photosensitive resin composition I according to the presentinvention and may be optionally incorporated in each one of thephotosensitive resin compositions II, III and IV according to thepresent invention.

No special limitation is imposed on the zinc compound (C1), and it canbe synthesized from zinc and an acid such as molybdic acid, phosphoricacid, hexahydrooxostannic acid, stannic acid, and boric acid. Examplesof the zinc compound include calcium zinc molybdate, zinc molybdate,zinc oxide, zinc phosphate, zinc hexahydrooxostannate, zinc stannate,and zinc borate, with zinc molybdate, zinc stannate, and zinc boratebeing preferred. These compounds may be used singly or with two or morein combination. The above-mentioned zinc compound is preferably coatedonto fillers such as talc by wet process and the like, in view of costs.

Examples of available zinc compound include KEMGARD911A, KEMGARD911B,KEMGARD911C, KEMGARD981, KEMGARD425 (product names of Sherwin-WilliamsJapan Co., Ltd.), FLAMTARD-H, FLAMTARD-S (product names of Nippon LightMetal Co., Ltd.) and HA-1, SZB-2335, HA-S1, and HA-1T (product names ofSakai Chemical Industry Co., Ltd.).

The above-mentioned component (C1) is preferably used in an amount of0.5% or more by weight in view of the flame retardancy of the resultantcured material, preferably 20% or less by weight in terms of the heatresistance, and more preferably 1 to 15% by weight, based on the totalamount of the photosensitive resin composition.

The above-mentioned organic nitrogen-based compound (C2) is used as anessential component in the photosensitive resin composition II accordingto the present invention, and may be optionally incorporated into eachone of the photosensitive resin compositions I, III and IV according tothe present invention.

The organic nitrogen-based compound (C2) is an organic compound havingone or more nitrogen atoms in the molecule, and is preferably an organiccompound having at least three nitrogen atoms in the molecule, and morepreferably a triazine-based compound having a six-member ring structurehaving three nitrogen atoms in the molecule (triazine ring includinghydrotriazine ring).

As a triazine-based compound, melamine phenol compounds with repeatingunits represented by the general formulae (Ia) and (Ib) and melaminephenol compounds with repeating units represented by the generalformulae (Ic) and (Id) are preferably used.

(wherein R represents a divalent organic group)

(wherein R′ represents a divalent organic group and Z represents —NH₂,

or an aryl group having 6 to 18 carbon atoms)

(wherein R¹ represents a hydrogen atom or a methyl group)

(wherein Z is the same as Z in the above-mentioned general formula(Ib)).

Moreover, examples of the above-mentioned triazine-based compoundinclude melamine acrylate compounds represented by the general formula(II):

(wherein each one of six A independently represents a (meth)acryloylgroup and each one of six R² independently represents a divalent organicgroup) triazine derivatives represented by the general formula (III):

(wherein R³ represents a monovalent aliphatic group having 1 to 10carbon atoms or an aryl group having 6 to 18 carbon atoms) triazinederivatives represented by the general formula (IV):

(wherein R⁴ represents a divalent aliphatic group having 1 to 10 carbonatoms or an arylene group having 6 to 18 carbon atoms) isocyanuratederivatives represented by the general formula (V):

(wherein each one of three R⁵ independently represents a hydrogen atomor a methyl group) isocyanurate derivatives represented by the generalformula (VI):

(wherein each one of three R⁶ independently represents a hydrogen atomor a methyl group and each one of three R⁷ independently represents analkylene group having 1 to 10 carbon atoms) triazine derivativesrepresented by the general formula (VII):

(wherein each one of six R⁸ independently represents an alkyl grouphaving 1 to 10 carbon atoms) triazine derivatives represented by thegeneral formula (VIII):

(wherein each one of m¹ to m⁶ is independently 0, 1, or 2 and(m¹+m²)=(m³+m⁴)=(m⁵+m⁶)=2) triazine derivatives represented by thegeneral formula (IX):

(wherein each one of six R⁵ is independently identical to R⁵ in theabove-mentioned general formula (V)) melamine formaldehyde resins whichare copolymers of 1,3,5-triaminotriazine and formaldehyde, melaminephosphate compounds which are copolymers of 1,3,5-triaminotriazine andphosphoric acid, compounds of 1,3,5-triaminotriazine and pyrophosphoricacid, sulfuric acid-2-melamine, melamine resins which are copolymers ofbenzoguanamine and formaldehyde, melamine polyphosphate, triglycidylisocyanurate, and 1,3,5-triaminotriazine. These compounds may be usedsingly or with two or more in combination. 1,3,5-Triaminotriazine ispreferably used in view of adhesion of the photosensitive resincomposition film. Triazine derivatives represented by the generalformula (III), which can preferably be benzoguanamine (a compound of thegeneral formula (III) with R³ being a phenyl group), for example, arepreferably used in view of availability.

In view of flame retardancy, preferred compounds include melamine phenolcompounds represented by the general formulae (Ia) to (Id), melamineacrylate compounds represented by the general formula (III), triazinederivatives represented by the general formula (IV), isocyanuratederivatives represented by the general formula (V), isocyanuratederivatives represented by the general formula (VI), triazinederivatives represented by the general formula (VII), triazinederivatives represented by the general formula (VIII), triazinederivatives represented by the general formula (IX), melamine phosphatecompounds which are copolymers of 1,3,5-triaminotriazine and phosphoricacid, melamine formaldehyde resins which are copolymers of1,3,5-triaminotriazine and formaldehyde, compounds obtained by thereaction of 1,3,5-triaminotriazine and pyrophosphoric acid, sulfuricacid-2-melamine, melamine resins which are copolymers of benzoguanamineand formaldehyde, melamine polyphosphate, triglycidyl isocyanurate andthe like.

No specific limitation is imposed on the melamine phenol compounds withrepeating units represented by the general formulae (Ia) to (Id),provided at least one melamine unit and at least one phenol unit arepresent in the molecule. Furthermore, when a repeating number ofmelamine units and phenol units is plural, the melamine units and thephenol units may be linked either as blocks or in a randomconfiguration.

Examples of the alkyl group having 1 to 10 carbon atoms in the generalformulae (I) to (IX) include a methyl group, an ethyl group, an n-propylgroup, an isopropyl group, an n-butyl group, an isobutyl group, asec-butyl group, a tertbutyl group, a pentyl group, an isopentyl group,a neopentyl group, a hexyl group, a heptyl group, an octyl group, anonyl group, a decyl group, and structural isomers thereof.

Examples of the alkylene group having 1 to 10 carbon atoms in thegeneral formulae (I) to (IX) include a methylene group, an ethylenegroup, an n-propylene group, an isopropylene group, an n-butylene group,an isobutylene group, a sec-butylene group, a tert-butylene group, apentylene group, an isopentylene group, a neopentylene group, a hexylenegroup, a heptylene group, an octylene group, a nonylene group, adecylene group, and structural isomers thereof.

Examples of the aryl group having 6 to 18 carbon atoms in the generalformulae (I) to (IX) include a phenyl group, a tolyl group, a xylylgroup, a biphenyl group, a naphthyl group, an anthryl group, and aphenanthryl group, and these groups may be substituted with a halogenatom, an amino group, a nitro group, a cyano group, a mercapto group, anallyl group, or an alkyl group having 1 to 20 carbon atoms.

Examples of the arylene group having 6 to 18 carbon atoms in the generalformulae (I) to (IX) include a phenylene group, a tolylene group, axylylene group, a biphenylene group, a naphthylene group, an anthrylenegroup, and a phenanthrylene group, and these groups may be substitutedwith a halogen atom, an amino group, a nitro group, a cyano group, amercapto group, an allyl group, or an alkyl group having 1 to 20 carbonatoms.

The compounds represented by the general formulae (I) to (IX) may besubstituted with a substitutable substituent such as an amino group, anitro group, a cyano group, a mercapto group, an allyl group, or analkyl group having 1 to 20 carbon atoms.

Examples of available organic nitrogen-based compound (C2) include1,3,5-triaminotriazine, benzoguanamine,1,3,5-triacryloylhexahydro-S-trizine (TAF), tris(acryloxyethyl)isocyanurate (a compound of the general formula (VI) with R⁶ being ahydrogen atom and R⁷ being an ethyl group), tris(methacryloxyethyl)isocyanurate (a compound of the general formula (VI) with R⁶ being amethyl group and R⁷ being an ethyl group), caprolactone-modifiedtris(acryloxyethyl) isocyanurate, hexamethoxymelamine,hexabutoxymelamine, hexamethylolmelamine, N-3A, N-6A, N-6M (productnames of Shin-Nakamura Chemical Co., Ltd.), SetaCure 590, SetaCure 591(product names of Akzo Nobel KK), Melapur 200, Melapur MC15 (productnames of DSM Japan), SG102, SGO-201 (product names of ShikokuCorporation), Apinon901, P-7202, MPP-A, SB-201, SB-202, SB-203, SB-254,SB-255, SB-301, SB-302, SB-303, SB-354, SB-355 (product names of SanwaChemical Co., Ltd.), Planelon NP (product name of Mitsui Kagaku FineChemicals, Inc.), Cymel 300, Cymel 301, Cymel 303, Cymel 325, Cymel 350,Cymel 370, Cymel 1123 (product names of Mitsui Cytech Ltd.), MELAN 523,MELAN 2000, MELAN 3000 (product names of Hitachi Chemical Co., Ltd.),Melem (product name of Nissan Chemical Industries, Ltd., a compound ofthe general formula (IX) with R⁵ being a hydrogen atom), PMP-100,PMP-200, and PMP-300 (product names of Nissan Chemical Industries, Ltd.,melamine polyphosphate). These compounds may be used singly or with twoor more in combination.

The component (C2) is used preferably in an amount of 0.2% or more byweight in view of the flame retardancy of the resultant cured film,preferably 10% or less by weight in view of heat resistance, and morepreferably 0.5 to 8% by weight, based on the total amount of thephotosensitive resin composition.

The above-mentioned metal hydroxide (C3) is used in the photosensitiveresin composition III according to the present invention as an essentialcomponent and may be optionally incorporated in each one of thephotosensitive resin compositions I, II and IV according to the presentinvention.

Examples of the metal hydroxide (C3) include aluminum hydroxide,magnesium hydroxide, aluminum hydroxide magnesium carbonate hydrate,nickel hydroxide, titanium hydroxide, and iridium hydroxide. Thesecompounds may be used singly or with two or more in combination.

The component (C3) is preferably used in an amount of 5% or more byweight in view of the flame retardancy of the resultant cured film,preferably 50% or less by weight in view of heat resistance, and morepreferably 10 to 40% by weight, based on the total amount of thephotosensitive resin composition.

The above-mentioned organic phosphorus-based compound (C4) is used inthe photosensitive resin composition IV according to the presentinvention as an essential component and may be optionally incorporatedin each one of the photosensitive resin compositions I, II and IIIaccording to the present invention.

The organic phosphorus-based compound (C4) is an organic compoundcontaining a phosphorus atom in the molecule, and examples of theorganic phosphorus-based compound include trimethyl phosphate, triethylphosphate, triphenyl phosphate, tricresyl phosphate, trixylenylphosphate, cresyl phenyl phosphate, cresyl di-2,6-xylenyl phosphate,2-methacryloyloxyethylacid phosphate, diphenyl-2-metacryloyloxyethylphosphate, phosphate-based compounds represented by the general formula(X):

(wherein each one of R⁹ to R²⁵ independently represents a hydrogen atomor an alkyl group having 1 to 10 carbon atoms; W represents a singlebond, an alkylene group having 1 to 10 carbon atoms, —S—, —SO₂—, —O—,—CO— or —N═N—; and n¹ is an integer greater than or equal to 1)phosphate-based compounds represented by the general formula (XI):

(wherein each one of R²⁶ to R⁴¹ independently represents a hydrogen atomor an alkyl group having 1 to 10 carbon atoms; and n² is an integergreater than or equal to 1) triaryl phosphate, and phosphorus-containingepoxy resins. These compounds may be used singly or with two or more incombination.

Examples of available organic phosphorus-based compound include aromaticpolyphosphates such as CR-733S, CR-741, CR-747, PX-200 (product names ofDaihachi Chemical Industry Co., Ltd.), SP-703, SP-601 (product names ofShikoku Corporation), and ‘REOFOS’ series 35, 50, 65, 95, and 110(product names of Ajinomoto Co., Inc.). Examples of thephosphorus-containing epoxy resins include ZX-1548 series 1, 2, 3, and 4(product names of Tohto Kasei Corporation). These compounds may be usedsingly or with two or more in combination.

The component (C4) is preferably used in an amount of 2% or more byweight in view of the flame retardancy of the resultant cured film,preferably 50% or less by weight in view of heat resistance, and morepreferably 5 to 40% by weight, based on the total amount of thephotosensitive resin composition.

The photosensitive resin composition of the present invention (that is,the above-mentioned composition X and compositions I to IV; the samealso applies hereinafter) may contain a curing agent (D) as required.The curing agent preferably cures itself by the action of heat orultraviolet or reacts with carboxyl groups, hydroxyl groups, and thelike of the photosensitive resin component in the photosensitive resincomposition of the present invention to cure by the action of heat orultraviolet. Use of the above-mentioned curing agent can improve theheat resistance, adhesion, chemical resistance etc. of the final curedfilm.

Examples of the above-mentioned curing agent (D) include epoxycompounds, urea compounds, and oxazoline compounds. Examples of theepoxy compounds include bisphenol A-type epoxy resins, bisphenol F-typeepoxy resins, hydrogenated bisphenol A-type epoxy resins, novolactype-epoxy resins, bisphenol S-type epoxy resins, heterocyclic epoxyresins such as triglycidyl isocyanurate, and bixylenol-type epoxy resinssuch as bixylenyl glycidyl ether of YX4000 (manufactured by Yuka ShellEpoxy Kabushiki Kaisha). Examples of the above-mentioned urea compoundsinclude dimethylol urea and the like. These compounds may be used singlyor with two or more in combination.

When the component (D) is to be incorporated, its content is preferably2% or more by weight in view of the heat resistance of the resultantcured film, preferably 50% or less by weight in view of developmentproperties, and more preferably 10 to 40% by weight, based on the totalamount of the photosensitive resin composition.

The photosensitive resin composition of the present invention maycontain an epoxy resin curing agent in order to improve variousproperties in the final cured film such as heat resistance, adhesion,chemical resistance and the like.

Examples of the epoxy resin curing agent include imidazoles such as2-methylimidazole, 2-ethyl-4-methylimidazole,1-benzyl-2-methylimidazole, 2-phenylimidazole, and2-phenyl-4-methyl-5-hydroxymethylimidazole; amines such asdiaminodiphenylmethane, phenylenediamine, xylylenediamine,diaminodiphenylsulfone, dicyandiamide, urea, and urea derivatives;organic acid salts or epoxy adducts thereof; amine complexes oftrifluoroborane; triazine derivatives such as ethyldiamino-S-triazine,2,4-diamino-S-triazine, and 2,4-diamino-6-xylyl-S-triazine; tertiaryamines such as triethylamine, triethanolamine, N,N-dimethyloctylamine,N-benzyldimethylamine, pyridine, N-methylmorpholine,hexa(N-methyl)melamine, 2,4,6-tris(dimethylaminophenol)melamine,tetramethylguanidine, and m-dimethylaminophenol; polyphenols such aspolyvinylphenol, phenol novolac, and alkylphenol novolac; and organicphosphines such as tributylphosphine, triphenylphosphine, andtris-2-cyanoethylphosphine. The epoxy resin curing agent is preferablyused in an amount of 0.01 to 20% by weight, and more preferably 0.1 to10% by weight, based on the total amount of the photosensitive resincomposition. These epoxy resin curing agents may be used singly or withtwo or more in combination.

Furthermore, a diluent can be used for the photosensitive resincomposition of the present invention as required. Organic solvents andphotopolymerizable compounds can be used, for example, as the diluent.For the organic solvent, the above-mentioned organic solvents used forthe reaction of the component (a1) and the component (a2) can be used.

For the photopolymerizable compounds, the following may be used:hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylates and2-hydroxypropyl (meth)acrylates; mono or di(meth)acrylates of glycolssuch as ethylene glycol, methoxytetraethylene glycol, and polyethyleneglycol; (meth)acrylamides such as N,N-dimethyl(meth)acrylamide andN-methylol(meth)acrylamide; aminoalkyl (meth)acrylates such asN,N-methylaminoethyl (meth)acrylate; polyvalent (meth)acrylates ofpolyols such as hexanediol, trimethylol propane, pentaerythritol,ditrimethylol propane, dipentaerythritol, and trishydroxyethylisocyanurate or ethylene oxide or propylene oxide adducts of thesepolyol; (meth)acrylates of ethylene oxide or propylene oxide adducts ofphenols such as phenoxyethyl (meth)acrylate and polyethoxydi(meth)acrylate of bisphenol A; and (meth)acrylates of glycidyl etherssuch as glycerin diglycidyl ether, trimethylol propane triglycidylether, and triglycidyl isocyanurate. These diluents may be used singlyor with two or more in combination.

When a diluent is to be used, its content is preferably 5% or more byweight in view of photosensitivity, preferably 80% or less by weight inview of heat resistance, and more preferably 10 to 70% by weight, basedon the total amount of the photosensitive resin composition.

The photosensitive resin composition of the present invention maycontain a known inorganic filler such as barium sulfate, bariumtitanate, silica, talc, calcined kaoline, magnesium carbonate, aluminumoxide, aluminum hydroxide, and mica, as required, in order to furtherimprove properties such as adhesion and the hardness of the film. Thefiller is preferably included in an amount of 2 to 80% by weight andmore preferably 5 to 50% by weight, based on the total amount of thephotosensitive resin composition. These fillers may be used singly orwith two or more in combination.

The photosensitive resin composition of the present invention maycontain well-known and conventionally used additives, for example aknown colorant such as phthalocyanine blue, phthalocyanine green, iodinegreen, disazo yellow, crystal violet, titanium oxide, carbon black, andnaphthalene black; a polymerization inhibitor such as hydroquinone,methylhydroquinone, hydroquinone monomethyl ether, catechol, andpyrogallol; a thickening agent such as bentone and montmorillonite; asilicone-based, fluorine-based, or vinyl resin-based anti-foaming agent;and a silane coupling agent, as required. These additives may be usedsingly or with two or more in combination.

In the present invention, it is preferable to use components such as theabove-mentioned additives that contain no halogen atoms or antimonyatoms. Else, the content of halogen atoms or antimony atoms ispreferably 1% or less by weight, and more preferably 0.5% or less byweight, based on the total solid content of the photosensitive resincomposition (when the composition contains solvents such as a diluent,the weight of the solvents are excluded and a dry weight is used).

The photosensitive resin composition of the present invention, whichcontains the components mentioned above, can be obtained, for example,by kneading and mixing the components to homogeneity with a roll mill, abead mill etc.

The resultant photosensitive resin composition is subjected to imageformation and used for the preparation of cured films as follows. Forexample, the photosensitive resin composition is applied for a thicknessof about 10 μm to about 200 μm onto a substrate such as flexible printedwiring boards by methods such as screen printing, spraying, rollcoating, curtain coating, and electrostatic coating. After the film isdried at about 60° C. to about 110° C., a negative film is placeddirectly onto the film (alternatively, via a transparent film) andactive rays such as ultraviolet ray is irradiated and unexposed portionsare removed by being dissolved in a dilute alkali aqueous solution(development).

The exposed portions are subjected to post exposure such as UV exposureor post heating, as required, to obtain a fully cured film. The postexposure is preferably conducted at about 1 J/cm to about 5 J/cm and thepost heating is preferably conducted at about 100° C. to about 200° C.for about 30 minutes to about 12 hours.

The layer of the photosensitive resin composition is laminated onto asubstrate to obtain a photosensitive element, as is described in detaillater.

The photosensitive resin composition of the present invention can beused in electric and electronic materials such as printed wiring boards,semiconductors and the like, and is suitable as a non-halogen,non-antimony-based photosensitive resin composition to be used as asolder mask resist, an interlayer insulating film (a build-up material),and a plating resist, which do not contain halogen-based compounds orantimony-based compounds and are superior in flame retardancy, heatresistance, mechanical properties, adhesion, and chemical resistance, inapplications such as wiring boards for ball grid array, wiring boardsfor chip size package, flexible printed wiring boards, high-densitymulti-layer substrates, and tape carriers.

Next, the photosensitive element according to the present invention,i.e., a photosensitive element obtained by forming a resist layer formedby any one of the above-mentioned photosensitive resin composition X andthe photosensitive resin compositions I to IV onto a substrate, will bedescribed with reference to the drawings.

FIG. 1 schematically shows an embodiment of the photosensitive element,in which the photosensitive element 1 contains a substrate 11 and aresist layer (the photosensitive resin composition layer) 12 formedthereon. For the substrate 11, a polymer film such as polyethyleneterephthalate, polypropylene, polyethylene, and polyester can suitablybe used. The polymer film is preferably about 5 μm to about 100 μmthick. Although no special limitation is imposed on the method offorming the resist layer 12 onto the substrate 11, the resist layer 12can preferably be obtained by coating a solution of the photosensitiveresin composition and then drying. The thickness of the photosensitiveresin composition coated varies depending on the application and ispreferably about 10 μto about 100 μm after drying. The coating can beconducted by the known method such as roll coater, comma coater, gravurecoater, air-knife coater, die coater, bar coater, and the like. Thedrying can be performed at about 70° C. to about 150° C. for about 5minutes to about 30 minutes. The amount of the organic solvent left inthe resist layer 12 is preferably 2% or less by weight in order toprevent diffusion of the organic solvent in subsequent steps. Thesurface of the resist layer may be coated with a protective filmcomprising a polymer film such as polyethylene and polypropylene.

The method of producing a resist pattern according to the presentinvention will next be described with reference to FIG. 2, whichschematically shows an example of the steps.

Firstly, a resist layer formed by any one of the above-mentionedphotosensitive resin composition X and the photosensitive resincompositions I to IV is laminated onto a substrate as a step (i). Anylamination methods may be used, and for example, as shown in FIG. 2(A)the above-mentioned photosensitive element 1 is laminated onto asubstrate 2 that contains a base 21 comprising a glass fiber-filledepoxy resin and the like with a layer-to-be-processed 22 comprisingcopper and the like formed thereon, such that the resist layer 12adheres to the surface of the layer-to-be-processed 22. When aprotective film (not shown) is present on the resist layer 12 of thephotosensitive element 1, the protective layer is removed beforelamination. The lamination method can be, for example, such that theresist layer 12 is contact-bonded to the substrate 2 under a pressure ofabout 0.1 MPa to about 1 MPa (about 1 kgf/cm² to about 10 kgf/cm²) whilebeing heated to about 70° C. to about 130° C. Lamination under reducedpressure is also employable.

After the lamination of the resist layer is completed, active rays areirradiated in an image shape to photo-cure the resist layer at exposedportions as step (ii). An example of the method of irradiating activerays in an image shape utilizes active rays being irradiated through amask pattern 3 to the resist layer 12 in an image shape to photo-curethe exposed portions of the resist layer 12, as shown in FIG. 2(B). Themask pattern 3 may be either negative-type or positive-type, and thosegenerally used can be used. As the light source of the active rays,known light sources which effectively radiate ultraviolet rays, visiblerays, and the like such as carbon arc lamp, mercury-vapor lamp, highpressure mercury vapor lamp, xenon lamp, and the like are employable.Alternatively, a laser beam direct imaging method is also applicable inwhich no mask pattern is needed.

After the exposure, as step (iii), the resist layer at unexposedportions is selectively removed by development to form a resist pattern121 as shown in FIG. 2(C). The exposure in the step (ii) can beperformed in the presence of the support 11 provided the support doesnot interfere with irradiation to the resist layer 12, in which case thesupport 11 is removed before the development. The development isperformed by removing the unexposed portions by wet development withdevelopers such as alkaline aqueous solutions, water-based developers,organic solvents etc., dry development, and the like. Theabove-mentioned alkaline aqueous solutions are preferably used and theirexamples include 0.1 to 5% by weight dilute solutions of sodiumcarbonate, 0.1 to 5% by weight dilute solutions of potassium carbonate,and 0.1 to 5% by weight dilute solutions of sodium hydroxide. The pH ofthe alkaline aqueous solutions is preferably adjusted to the range of 9to 11, and the temperature is adjusted to the development properties ofthe layer of the photosensitive resin composition. The alkaline aqueoussolution may contain a surfactant, an antifoaming agent, an organicsolvent, etc. Methods for the above-mentioned development can be any oneof dipping-method, spray-method, brushing, and slapping, for example.

As a post-development treatment, heating to about 60° C. to about 250°C. or exposure in about 0.2 J/cm² to about 10 J/cm² may be conducted asrequired to further cure the resultant resist pattern.

The resist pattern laminated substrate according to the presentinvention is obtained by laminating the resist pattern obtained usingthe resist layer formed by any one of the above-mentioned photosensitiveresin compositions X and I to IV according to the present invention ontoa substrate. The laminated substrate can be produced by any knownmethods.

The present invention will next be described in further detail withreference to examples. ‘Parts’ in SYNTHESIS EXAMPLES and EXAMPLES referto parts by weight.

SYNTHESIS EXAMPLE 1

220 Parts of YDCN704 (manufactured by Tohto Kasei Corporation, a cresolnovolac-type epoxy resin), 72 parts of acrylic acid, 1.0 part ofhydroquinone, and 180 parts of carbitol acetate were mixed, heated to90° C., and stirred to dissolve the reaction mixture.

The resultant mixture was then cooled to 60° C., and 1 part ofbenzyltrimethylammonium chloride was added to the mixture, which washeated to 100° C. and allowed to react till the acid value reached 1mgKOH/g.

Subsequently, 152 parts of tetrahydrophthalic anhydride and 100 parts ofcarbitol acetate were added to the mixture, which was heated to 80° C.,reacted for 6 hours, and diluted with carbitol acetate to adjust thesolid content to 60% to obtain a photosensitive resin P1.

SYNTHESIS EXAMPLE 2

330 Parts of EPPN502H (manufactured by Nippon Kayaku Co., Ltd., asalicylic aldehyde-type epoxy resin), 144 parts of acrylic acid, 1.5part of hydroquinone, and 250 parts of carbitol acetate were mixed,heated to 90° C., and stirred to dissolve the reaction mixture.

The resultant mixture was then cooled to 60° C., and 2 parts ofbenzyltrimethylammonium chloride were added to the mixture, which washeated to 100° C. and allowed to react till the acid value reached 1mgKOH/g.

Subsequently, 230 parts of tetrahydrophthalic anhydride and 180 parts ofcarbitol acetate were added to the mixture, which was heated to 80° C.,reacted for 6 hours, and diluted with carbitol acetate to adjust thesolid content to 60% to obtain a photosensitive resin P2.

SYNTHESIS EXAMPLE 3

475 Parts of YDF2001 (manufactured by Tohto Kasei Corporation, abisphenol F-type epoxy resin), 72 parts of acrylic acid, 0.5 part ofhydroquinone, and 120 parts of carbitol acetate were mixed, heated to90° C., and stirred to dissolve the reaction mixture.

The resultant mixture was then cooled to 60° C., and 2 parts ofbenzyltrimethylammonium chloride were added to the mixture, which washeated to 100° C. and allowed to react till the acid value reached 1mgKOH/g.

Subsequently, 98 parts of maleic anhydride and 85 parts of carbitolacetate were added to the mixture, which was heated to 80° C., reactedfor 6 hours, and diluted with carbitol acetate to adjust the solidcontent to 60% to obtain a photosensitive resin P3.

EXAMPLES 1 TO 32 and COMPARATIVE EXAMPLES 1 TO 4

Components were mixed according to the formulation shown in Table 1 andkneaded with a triple roll mill to obtain compositions.

Each composition was coated onto a copper-clad laminate (MCL-RO-67G, 0.3mm thick, manufactured by Hitachi Chemical Co., Ltd.) using a 120-meshTetron screen by screen printing such that it had a thickness of 30 μmafter drying, which was dried in a convection type drier at 80° C. for30 minutes.

Then, a negative mask with a predetermined pattern was allowed to adhereto the coating, which was then subjected to ultraviolet ray in 500mJ/cm² by a UV exposing equipment.

Subsequently, spray development was conducted by spraying 1% sodiumcarbonate aqueous solution at a pressure of 0.18 MPa for 60 seconds todissolve and remove unexposed portions.

The resultant image was evaluated for development properties andphotosensitivity, and then heated at 150° C. for 1 hour to prepare atest board.

Each test board was tested for adhesion, acid resistance, alkaliresistance, solder thermal resistance, and thermal shock resistance, asdescribed hereinafter. Table2 summarizes the test results.

The test methods and evaluation methods are as follows.

[Adhesion]

A pattern of one hundred 1 mm-square checks was formed on each testpiece according to the Japanese Industrial Standards (JIS) K5400, andthe test piece was subjected to a peeling test using cellophane tape.The number of checks that peeled off was counted and graded according tothe following standards.

A: The number of remaining checks is greater than or equal to ninety outof one hundred checks.

B: The number of remaining checks is greater than or equal to fifty andsmaller than ninety, out of one hundred checks.

C: The number of remaining checks is greater than or equal to zero andsmaller than fifty, out of one hundred checks.

[Acid Resistance]

Each test piece was immersed in 10% hydrochloric acid aqueous solutionat room temperature for 30 minutes and a pattern of one hundred 1mm-square checks was formed on each test piece according to JIS K5400,and the test piece was subjected to a peeling test using cellophanetape. The number of checks that peeled off was counted and gradedaccording to the following standards.

A: The number of remaining checks is greater than or equal to ninety outof one hundred checks.

B: The number of remaining checks is greater than or equal to fifty andsmaller than ninety, out of one hundred checks.

C: The number of remaining checks is greater than or equal to zero andsmaller than fifty, out of one hundred checks.

[Alkali Resistance]

Each test piece was immersed in 5% sodium hydroxide aqueous solution atroom temperature for 30 minutes and a pattern of one hundred 1 mm-squarechecks was formed on each test piece according to JIS K5400, and thetest piece was subjected to a peeling test using cellophane tape. Thenumber of checks that peeled off was counted and graded according to thefollowing standards.

A: The number of remaining checks is greater than or equal to ninety outof one hundred checks.

B: The number of remaining checks is greater than or equal to fifty andsmaller than ninety, out of one hundred checks.

C: The number of remaining checks is greater than or equal to zero andsmaller than fifty, out of one hundred checks.

[Solder Thermal Resistance]

A test piece was coated with a rosin-based flux or a water-soluble fluxand immersed in a solder bath at 260° C. for 10 seconds, which was takenas a cycle. Each test piece was subjected to six cycles and visuallyinspected to evaluate the appearance of the coating.

A: No change (peeling or blister) was shown on the coating and there wasno creeping of solder.

B: A change (peeling or blister) or creeping of solder was shown on thecoating.

[Thermal Shock Resistance]

Each test piece was subjected to a thermal hysteresis of 1000 cycles, acycle being −55° C./30 minutes and 125° C./30 minutes, after which thetest piece was visually and microscopically inspected.

A: No cracks found.

B: Cracks found.

[Flame Retardancy]

A substrate, a non-halogen copper-clad laminate (MCL-RO-67G, 0.3 mmthick) was coated with the resist at a thickness of 50 μm on both sides,from which a test piece defined in UL94V was prepared and subjected to avertical burning test according to UL94V standards.

A: The fire did not remain till a clamp and was extinguished within 10seconds and the test piece did not drop flaming particles which set afire to cotton placed 305 mm below (which means achievement of UL94V-0).

B: The fire did not remain till a clamp and was extinguished within 30seconds and the test piece did not drop flaming particles which set afire to cotton placed 305 mm below (which means achievement of UL94V-1).

C: The test piece achieved neither UL94-0 nor UL94-1.

TABLE 1-1 Examples Component/% by weight 1 2 3 4 5 6 7 8 9 10 11 12 APhotosensitive Resin P1 70 0 0 0 0 70 70 70 0 0 0 0 Photosensitive ResinP2 0 70 0 0 0 0 0 0 70 0 0 0 Photosensitive Resin P3 0 0 70 0 0 0 0 0 070 0 0 ZFR1122 0 0 0 70 0 0 0 0 0 0 70 0 ZFR1179 0 0 0 0 70 0 0 0 0 0 070 B Irgacure 907 5 5 5 5 5 5 5 5 5 5 5 5 KAYACURE DETX-S 0.5 0.5 0.50.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 C1 KEMGARD911A 5 0 0 0 5 0 0 5 0 0 05 KEMGARD911C 0 5 0 0 0 5 0 0 5 0 0 0 FLAMTARD-H 0 0 5 0 0 0 5 0 0 5 0 0HA-1 0 0 0 5 0 0 0 0 0 0 5 0 C2 1,3,5-triaminotriazine 5 0 0 0 0 0 0 3 33 3 3 SG-102 0 5 0 0 0 0 0 0 0 0 0 0 SGO-201 0 0 5 0 0 0 0 0 0 0 0 0Melapur200 0 0 0 5 0 0 0 0 0 0 0 0 MPP-A 0 0 0 0 5 0 0 0 0 0 0 0Planelon NP 0 0 0 0 0 5 0 0 0 0 0 0 N-3A 0 0 0 0 0 0 5 0 0 0 0 0Hexahydrotriazine D* 0 0 0 0 0 0 0 0 0 0 0 0 C3 Aluminum hydroxide 30 3030 30 10 10 10 0 0 0 5 5 C4 CR-747 0 0 0 0 0 0 0 5 0 0 0 0 PX-200 0 0 00 0 0 0 0 5 0 0 0 ZX-1548-3 0 0 0 0 0 0 0 0 0 5 0 0 SP-703 0 0 0 0 0 0 00 0 0 5 0 REOFOS 110 0 0 0 0 0 0 0 0 0 0 0 5 D Epikote 828 6 6 6 6 6 6 66 6 6 6 6 Colorant Phthalocyanine Blue 1 1 1 1 1 1 1 1 1 1 1 1 FrameAntimony trioxide 0 0 0 0 0 0 0 0 0 0 0 0 retardant BREN-S 0 0 0 0 0 0 00 0 0 0 0 EBR-100 0 0 0 0 0 0 0 0 0 0 0 0 Diluent KAYARAD DPHA 5 5 5 5 55 5 5 5 5 5 5 Filler Silica 0 0 0 0 10 10 10 20 20 20 15 15 Bariumsulfate 0 0 0 0 10 10 10 10 10 10 10 10 Hexahydrotriazine D*:1,3,5-triacryloylhexahydro-S-triazine

TABLE 1-2 Examples Component/% by weight 13 14 15 16 17 18 19 20 21 2223 24 A Photosensitive Resin P1 70 0 0 0 70 0 0 0 70 0 0 0Photosensitive Resin P2 0 70 0 0 0 70 0 0 0 70 0 0 Photosensitive ResinP3 0 0 70 0 0 0 70 0 0 0 70 0 ZFR1122 0 0 0 0 0 0 0 0 0 0 0 0 ZFR1179 00 0 70 0 0 0 70 0 0 0 70 B Irgacure 907 4 4 4 4 4 4 4 4 5 5 5 5 KAYACUREDETX-S 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 C1 KEMGARD911A 50 0 5 5 0 0 5 5 0 0 5 KEMGARD911C 0 0 0 0 0 0 0 0 0 0 0 0 FLAMTARD-H 0 00 0 0 0 0 0 0 0 0 0 HA-1 0 0 0 0 0 0 0 0 0 0 0 0 C21,3,5-triaminotriazine 0 0 0 0 0 0 0 0 5 0 0 0 SG-102 0 0 0 0 0 0 0 0 05 0 0 SGO-201 0 0 0 0 0 0 0 0 0 0 5 0 Melapur200 5 5 5 5 0 0 0 0 0 0 0 0MPP-A 0 0 0 0 0 0 0 0 0 0 0 5 Planelon NP 0 0 0 0 0 0 0 0 0 0 0 0 N-3A 00 0 0 5 5 0 0 0 0 0 0 Hexahydrotriazine D* 0 0 0 0 0 0 5 5 0 0 0 0 C3Aluminum hydroxide 30 30 30 30 30 30 30 30 30 30 30 10 C4 CR-747 5 5 5 05 5 5 0 5 5 5 0 PX-200 0 0 0 0 0 0 0 0 0 0 0 0 ZX-1548-3 0 0 0 0 0 0 0 00 0 0 0 SP-703 0 0 0 0 0 0 0 0 0 0 0 0 REOFOS 110 0 0 0 0 0 0 0 0 0 0 00 D Epikote 828 6 6 6 6 6 6 6 6 6 6 6 6 Colorant Phthalocyanine Blue 1 11 1 1 1 1 1 1 1 1 1 Frame Antimony trioxide 0 0 0 0 0 0 0 0 0 0 0 0Retardant BREN-S 0 0 0 0 0 0 0 0 0 0 0 0 EBR-100 0 0 0 0 0 0 0 0 0 0 0 0Diluent KAYARAD DPHA 4 4 4 4 4 4 4 4 5 5 5 5 Filler Silica 0 0 0 0 0 0 00 0 0 0 10 Barium sulfate 0 0 0 0 0 0 0 0 0 0 0 10 Hexahydrotriazine D*:1,3,5-triacryloylhexahydro-S-triazine

TABLE 1-3 Examples Comparative Examples Component/% by weight 25 26 2728 29 30 31 32 1 2 3 4 A Photosensitive Resin P1 70 70 70 70 0 70 70 7070 0 70 0 Photosensitive Resin P2 0 0 0 0 70 0 0 0 0 70 0 70Photosensitive Resin P3 0 0 0 0 0 0 0 0 0 0 0 0 ZFR1122 0 0 0 0 0 0 0 00 0 0 0 ZFR1179 0 0 0 0 0 0 0 0 0 0 0 0 B Irgacure 907 5 5 5 4 4 5 5 5 55 5 5 KAYACURE DETX-S 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 C1KEMGARD911A 0 0 0 0 0 5 0 0 0 0 0 0 KEMGARD911C 0 0 0 0 0 0 0 0 0 0 0 0FLAMTARD-H 0 0 0 0 0 0 0 0 0 0 0 0 HA-1 0 0 0 0 0 0 0 0 0 0 0 0 C21,3,5-triaminotriazine 0 0 5 5 5 0 0 0 0 0 0 5 SG-102 0 0 0 0 0 0 0 0 00 0 0 SGO-201 0 0 0 0 0 0 0 0 0 0 0 0 Melapur200 0 0 0 0 0 0 0 0 0 0 0 0MPP-A 0 0 0 0 0 0 0 0 0 0 0 0 Planelon NP 5 0 0 0 0 0 0 0 0 0 0 0 N-3A 05 0 0 0 0 0 0 0 0 0 0 Hexahydrotriazine D* 0 0 0 0 0 0 0 0 0 0 0 0 C3Aluminum hydroxide 10 10 0 0 0 0 10 0 0 0 0 0 C4 CR-747 0 0 0 0 0 0 0 50 0 0 0 PX-200 0 0 0 0 0 0 0 0 0 0 0 0 ZX-1548-3 0 0 0 0 0 0 0 0 0 0 0 0SP-703 0 0 0 0 0 0 0 0 0 0 0 0 REOFOS 110 0 0 0 0 0 0 0 0 0 0 0 0 DEpikote 828 6 6 6 6 6 6 6 6 6 6 6 6 Colorant Phthalocyanine Blue 1 1 1 11 1 1 1 1 1 1 1 Frame Antimony trioxide 0 0 0 0 0 0 0 0 0 5 0 5retardant BREN-S 0 0 0 0 0 0 0 0 0 0 0 10 EBR-100 0 0 0 0 0 0 0 0 0 0 50 Diluent KAYARAD DPHA 5 5 5 4 4 5 5 5 5 5 5 5 Filler Silica 10 10 20 1515 20 20 20 20 20 20 20 Barium sulfate 10 10 10 15 15 10 10 10 10 10 1010 Hexahydrotriazine D*: 1,3,5-triacryloylhexahydro-S-triazine

TABLE 2 Examples Evaluation 1 2 3 4 5 6 7 8 9 10 11 12 Halogencontent/wt % 0 0 0 0 0 0 0 0 0 0 0 0 Antimony content/wt % 0 0 0 0 0 0 00 0 0 0 0 Adhesion A A A A A A A A A A A A Acid resistance A A A A A A AA A A A A Alkali resistance A A A A A A A A A A A A Solder thermalresistance A A A A A A A A A A A A Thermal shock resistance A A A A A AA A A A A A Frame retardancy A A A A A A A A A A A A Examples Evaluation13 14 15 16 17 18 19 20 21 22 23 24 Halogen content/wt % 0 0 0 0 0 0 0 00 0 0 0 Antimony content/wt % 0 0 0 0 0 0 0 0 0 0 0 0 Adhesion A A A A AA A A A A A A Acid resistance A A A A A A A A A A A A Alkali resistanceA A A A A A A A A A A A Solder thermal resistance A A A A A A A A A A AA Thermal shock resistance A A A A A A A A A A A A Frame retardancy A AA A A A A A A A A A Examples Comparative Examples Evaluation 25 26 27 2829 30 31 32 1 2 3 4 Halogen content/wt % 0 0 0 0 0 0 0 0 0 0 41  35 Antimony content/wt % 0 0 0 0 0 0 0 0 0 84  0 84  Adhesion A A A A A A AA A A A A Acid resistance A A B B B B B B C C C A Alkali resistance A AA A A A A A A A A A Solder thermal resistance A A A A A A A A A A A AThermal shock resistance A A A A B A A A A B A B Frame retardancy A A BB B A A A C A A A Note: Each one of the contents of halogen and antimonyin the table shows a content of corresponding atoms in the frameretardant.

Each component shown in Formulation Table will be described as below.

ZFR1122: acid-containing epoxy resin (manufactured by Nippon Kayaku Co.,Ltd., solid content of 60% by weight)

ZFR1179: acid-containing rubber-modified epoxy resin (manufactured byNippon Kayaku Co., Ltd., solid content of 60% by weight)

Irgacure 907: 2-methy-[4-(methylthio)phenyl]morpholino-1-propanone(manufactured by Ciba Specialty Chemicals in Japan)

KAYACURE DETX-S: 2,4-diethylthioxanthone (manufactured by Nippon KayakuCo., Ltd.,)

KEMGARD911A: zinc molybdate compound (manufactured by Sherwin-WilliamsJapan Co., Ltd.)

KEMGARD911C: zinc molybdate compound (manufactured by Sherwin-WilliamsJapan Co., Ltd.)

FLAMTARD-H: zinc stannate compound (manufactured by Nippon Light MetalCo., Ltd.)

HA-1: zinc borate compound (manufactured by Sakai Chemical Industry Co.,Ltd.)

SG-102: triazine derivative (manufactured by Shikoku Corporation)

SGO-201: triazine derivative (manufactured by Shikoku Corporation)

Melapur 200: copolymer of 1,3,5-triaminotriazine and phosphoric acid(manufactured by DSM Japan)

MPP-A: melamine phosphate derivative (manufactured by Sanwa ChemicalCo., Ltd.)

Planelon NP: triazine derivative (manufactured by Mitsui Kagaku FineChemicals, Inc.)

N-3A: melamine acrylate (manufactured by Shin-Nakamura Chemical Co.,Ltd.)

Epikote 828: bisphenol A-type epoxy resin (manufactured by Yuka ShellEpoxy Kabushiki Kaisha)

BREN-S: bromine-containing epoxy resin (manufactured by Nippon KayakuCo., Ltd.; bromine content of 35% by weight)

EBR-100: brominated bisphenol A-type epoxy acrylate resin (manufacturedby MANAC Corporation; bromine content of 41% by weight)

KAYARAD DPHA: dipentaerythritol pentaacrylate (manufactured by NipponKayaku Co., Ltd.)

CR-747: phosphate compound (manufactured by Daihachi Chemical IndustryCo., Ltd.; a compound represented by the general formula (X) with R⁹ toR₁₂, R₁₄ to R¹⁹, and R²¹ to R₂₁₁ being a hydrogen atom and R¹³, R²⁰, andR²¹ being a methyl group, and W being a propylene group) PX-200:phosphate compound (manufactured by Daihachi Chemical Industry Co.,Ltd.)

ZX-1548-3: phosphorus-containing epoxy resin

(manufactured by Tohto Kasei Corporation)

SP-703: phosphate compound (manufactured by Shikoku Corporation)

REOFOS 110: phosphate compound (manufactured by Ajinomoto Co., Inc.)

The disclosure of the present application is related to the subjectmatter described in Japanese Patent Application No.11-300995 filed onOct. 22, 1999, Japanese Patent Application No.11-307516 filed on Oct.28, 1999, Japanese Patent Application No.11-307946 filed on Oct. 29,1999, Japanese Patent Application No.11-307947 filed on Oct. 29, 1999,and Japanese Patent Application No.2000-196492 filed on Jun. 29, 2000,the disclosure of which is incorporated herein by reference.

It is to be noted that, besides those already mentioned above, variouschanges and modifications can be made in the above-mentioned embodimentswithout departing from the novel and advantageous features of thepresent invention. Therefore, all such changes and modifications areintended to be included within the scope of the appended claims.

1. A photosensitive resin composition comprising a photosensitive resin(A), a photopolymerization initiator (B), and a flame retardant (C),wherein the photosensitive resin (A) is obtained by reacting a reactionProduct of epoxy resin (a1) and unsaturated group-containingmonocarboxylic acid (a2), with anhydride (a3) of saturated orunsaturated group-containing polybasic acid, and the epoxy resin (a1) isselected from the group consisting of novolac-type epoxy resins,bisphenol-type epoxy resins, salicylic aldehyde-type epoxy resins, andrubber-modified epoxy resins; the flame retardant (C) comprises a metalhydroxide (C3) and a triazine-based compound (C2), and the component(C3) is included in an amount of 10 to 40% by weight, and the component(C2) is included in an amount of 0.5 to 8% by weight, based on the totalamount of the composition.
 2. The photosensitive resin compositionaccording to claim 1, wherein the metal hydroxide (C3) is selected fromthe group consisting of aluminum hydroxide, magnesium hydroxide,aluminum hydroxide magnesium carbonate hydrate, nickel hydroxide,titanium hydroxide, and iridium hydroxide.
 3. The photosensitive resincomposition according to claim 1, further comprising an organicphosphorus-based compound (C4).
 4. The photosensitive resin compositionaccording to claim 1, wherein the component (A) is included in an amountof 10 to 90% by weight, and the component (B) is included in an amountof 0.5 to 20% by weight, based on the total amount of the composition.5. The photosensitive resin composition according to claim 3, wherein acontent of the component (C4) is 2 to 50% by weight based on the totalamount of the composition.
 6. The photosensitive resin compositionaccording to claim 3, wherein the organic phosphorus-based compound (C4)is selected from the group consisting of phosphate-based compoundsrepresented by the general formula (X):

(wherein each one of R⁹ to R²⁵ independently represents a hydrogen atomor an alkyl group having 1 to 10 carbon atoms; W represents a singlebond, an alkylene group having 1 to 10 carbon atoms, —S—, —SO₂—, —O—,—CO— or —N═N—; and n¹ is an integer greater than or equal to 1),phosphate-based compounds represented by the general formula (XI):

(wherein each one of R²⁶ to R⁴¹ independently represents a hydrogen atomor an alkyl group having 1 to 10 carbon atoms; and n² is an integergreater than or equal to 1), and phosphorus-containing epoxy resins. 7.The photosensitive resin composition according to claim 3, wherein acontent of the component (C4) is 2 to 50% by weight, based on the totalamount of the composition.
 8. The photosensitive resin compositionaccording to claim 1, further comprising a curing agent (D).
 9. Thephotosensitive resin composition according to claim 8, wherein a contentof the component (D) is 2 to 50% by weight based on the total amount ofthe composition.
 10. The photosensitive resin composition according toclaim 1, wherein the triazine-based compound is a melamine phenolcompound with repeating units represented by the general formulae (Ia)and (Ib):

(wherein R represents a divalent organic group)

(wherein R′ represents a divalent organic group and Z represents —NH₂,

or an aryl group having 6 to 18 carbon atoms).
 11. The photosensitiveresin composition according to claim 1, wherein the triazine-basedcompound is a melamine phenol compound with repeating units representedby the general formulae (Ic) and (Id):

(wherein R¹ represents a hydrogen atom or a methyl group)

(wherein Z represents —NH₂).
 12. The photosensitive resin compositionaccording to claim 1, wherein the triazine-based compound is a melamineacrylate compound represented by the general formula (II):

(wherein each one of six A independently represents a (meth)acryloylgroup and each one of six R² independently represents a divalent organicgroup).
 13. photosensitive resin composition according to claim 1,wherein the triazine-based compound is a triazine derivative representedby the general formula (III):

(wherein R³ represents a monovalent aliphatic group having 1 to 10carbon atoms or an aryl group having 6 to 18 carbon atoms).
 14. Thephotosensitive resin composition according to claim 1, wherein thetriazine-based compound is a triazine derivative represented by thegeneral formula (IV):

(wherein R⁴ represents a divalent aliphatic group having 1 to 10 carbonatoms or an arylene group having 6 to 18 carbon atoms).
 15. Thephotosensitive resin composition according to claim 1, wherein thetriazine-based compound is an isocyanurate derivative represented by thegeneral formula (V):

(wherein each one of three R⁵ independently represents a hydrogen atomor a methyl group).
 16. The photosensitive resin composition accordingto claim 1, wherein the triazine-based compound is an isocyanuratederivative represented by the general formula (VI):

(wherein each one of three R⁶ independently represents a hydrogen atomor a methyl group and each one of three R⁷ independently represents analkylene group having 1 to 10 carbon atoms).
 17. The photosensitiveresin composition according to claim 1, wherein the triazine-basedcompound is a triazine derivative represented by the general formula(VII):

(wherein each one of six R⁸ independently represents an alkyl grouphaving 1 to 10 carbon atoms).
 18. The photosensitive resin compositionaccording to claim 1, wherein the triazine-based compound is a triazinederivative represented by the general formula (VIII):

(wherein each one of m¹ to m⁶ is independently 0, 1, or 2 and(m¹+m²)=(m³+m⁴)=(m⁵+m⁶)=2).
 19. The photosensitive resin compositionaccording to claim 1, wherein the triazine-based compound is a triazinederivative represented by the general formula (IX):

(wherein each one of six R⁵ independently represents a hydrogen atom ora methyl group).
 20. The photosensitive resin composition according toclaim 1, wherein the triazine-based compound is selected from the groupconsisting of melamine formaldehyde resins which are copolymers of1,3,5-triaminotriazine and formaldehyde, melamine phosphate compoundswhich are copolymers of 1,3,5-triaminotriazine and phosphoric acid,compounds of 1,3,5-triaminotriazine and pyrophosphoric acid, sulfuricacid-2-melamine, melamine resins which are copolymers of benzoguanamineand formaldehyde, melamine polyphosphate, and triglycidyl isocyanurate.21. The photosensitive resin composition according to claim 1, whereinthe triazine-based compound is 1,3,5-triaminotriazine.
 22. Thephotosensitive resin composition according to claim 1, furthercomprising a zinc compound (C1).
 23. The photosensitive resincomposition according to claim 22, wherein the zinc compound (C1) issynthesized from an acid and zinc.
 24. The photosensitive resincomposition according to claim 23, wherein the acid is selected from thegroup consisting of molybdic acid, phosphoric acid, hexahydrooxostannicacid, stannic acid, and boric acid.
 25. The photosensitive resincomposition according to claim 22, wherein the zinc compound (C1) isselected from the group consisting of calcium zinc molybdate, zincmolybdate, zinc oxide, zinc phosphate, zinc hexahydrooxostannate, zincstannate, and zinc borate.
 26. The photosensitive resin compositionaccording to claim 22, further comprising an organic phosphorus-basedcompound (C4).
 27. The photosensitive resin composition according toclaim 22, wherein a content of the component (C1) is 0.5 to 20% byweight based on the total amount of the composition.
 28. Aphotosensitive element obtained by forming onto a substrate a resistlayer comprising a photosensitive resin composition according toclaim
 1. 29. A manufacturing method of a resist pattern comprising: i)laminating a resist layer comprising a photosensitive resin compositionaccording to claim 1 onto a substrate; ii) irradiating active rays in animage shape to photo-cure the resist layer at exposed portions; and iii)selectively removing the resist layer at unexposed portions bydevelopment to form a resist pattern.
 30. A resist pattern manufacturedby the manufacturing method of a resist pattern according to claim 29.31. A resist pattern laminated substrate obtained by laminating, onto asubstrate, a resist pattern obtained using a resist layer comprising aphotosensitive resin composition according to claim 1.